TWI608086B - A liquid crystal compound having bicyclo[3.3.0] octyl-7-ene-based structure, a liquid crystal composition comprising said compound and applicaton thereof - Google Patents

A liquid crystal compound having bicyclo[3.3.0] octyl-7-ene-based structure, a liquid crystal composition comprising said compound and applicaton thereof Download PDF

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TWI608086B
TWI608086B TW102136566A TW102136566A TWI608086B TW I608086 B TWI608086 B TW I608086B TW 102136566 A TW102136566 A TW 102136566A TW 102136566 A TW102136566 A TW 102136566A TW I608086 B TWI608086 B TW I608086B
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TW201414810A (en
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阮群奇
史志兵
房元飛
譚玉東
吳鳳
王毅明
丁豔
丁文全
王俊智
李清田
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江蘇和成顯示科技股份有限公司
達興材料股份有限公司
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Description

含雙環[3.3.0]辛-7-烯結構的液晶化合物、其液晶組合物和應用 Liquid crystal compound containing bicyclo[3.3.0]oct-7-ene structure, liquid crystal composition thereof and application thereof

本發明是有關於一種液晶化合物以及包括該液晶化合物的組合物和應用，特別是指一種新穎的含雙環[3.3.0]辛-7-烯結構的液晶化合物以及包括該液晶化合物的液晶組合物和應用。 The present invention relates to a liquid crystal compound and a composition and application comprising the same, and more particularly to a novel liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure and a liquid crystal composition comprising the liquid crystal compound And application.

物理學上把物質分為三態，即固態、液態和氣態。在自然界中，大部分材料隨溫度的變化只呈現固態、液態和氣態三種狀態，液晶(Liquid Crystal)是不同於通常的固態、液態和氣態的一種新的物質狀態，它能在某個溫度範圍內兼有液體和晶體兩者特性的物質狀態，也叫作液晶相或中間相，故又稱為物質的第四態。 Physically, the matter is divided into three states, namely solid, liquid and gaseous. In nature, most materials exhibit only three states of solid state, liquid state and gas state with temperature. Liquid crystal is a new material state different from the usual solid, liquid and gaseous states. It can be in a certain temperature range. The state of matter in which both the liquid and the crystal are characteristic, also referred to as the liquid crystal phase or the intermediate phase, is also referred to as the fourth state of matter.

液晶的種類很多，自然存在的和人工合成的液晶多達數千種，但他們基本上都是有機化合物。按液晶相形成的條件來歸納分類，液晶可以分為熱致型液晶、溶致型液晶、感應型液晶和流致型液晶。 There are many types of liquid crystals, and there are thousands of naturally occurring and synthetic liquid crystals, but they are basically organic compounds. According to the conditions formed by the liquid crystal phase, the liquid crystal can be classified into a thermotropic liquid crystal, a lyotropic liquid crystal, an inductive liquid crystal, and a flow-through liquid crystal.

目前，用於顯示的液晶材料基本上都是熱致型液晶。熱致型液晶因分子排列狀態的不同，可以分為近晶 相液晶(Smectic，又稱層狀液晶)、向列相液晶(Nematic，又稱絲狀液晶)、膽固醇相液晶(Cholesteric，也稱為螺旋狀液晶)。這些相的物理性質是已知的。用於光電領域的化合物的分子結構特徵，通常是有一個剛性骨架，其包含例如連接的1,4-伸苯基或1,4-伸環己基或雜環體系，其在相互間盡可能遠離的位置上被所謂的末端基團，如烷基、烷氧基或氰基取代。 Currently, liquid crystal materials for display are basically thermotropic liquid crystals. Thermotropic liquid crystals can be classified into smectic crystals due to different molecular arrangement states. Liquid crystal (Smectic, also known as lamellar liquid crystal), nematic liquid crystal (Nematic, also known as filamentous liquid crystal), cholesterol liquid crystal (Cholesteric, also known as spiral liquid crystal). The physical properties of these phases are known. Molecular structural features of compounds used in the field of optoelectronics, usually having a rigid backbone comprising, for example, linked 1,4-phenylene or 1,4-cyclohexylene or heterocyclic systems, as far as possible from each other The position is substituted by a terminal group such as an alkyl group, an alkoxy group or a cyano group.

用於光電領域的液晶組合物是由這些化合物混合組成，且其中也使用不具有從晶體相到液晶相互變轉化的化合物。按液晶顯示方式分類，液晶混合物可分為動態散射型(DS型)、主客型(GH型)、扭轉向列型(TN型)、超扭轉向列型(STN型)、薄膜電晶體型(TFT型)以及鐵電型(FLC型)等。液晶材料目前已經被廣泛的用於平板電腦、各種測定儀器、汽車用儀錶板、筆記型電腦、移動電話手機、電腦、電視機等液晶顯示元件的製作中。 The liquid crystal composition used in the field of optoelectronics is composed of a mixture of these compounds, and a compound which does not have a mutual transformation from a crystal phase to a liquid crystal is also used therein. According to the liquid crystal display method, the liquid crystal mixture can be classified into a dynamic scattering type (DS type), a host type (GH type), a twisted nematic type (TN type), a super twisted nematic type (STN type), a thin film transistor type ( TFT type) and ferroelectric type (FLC type). Liquid crystal materials have been widely used in the production of liquid crystal display elements such as tablet computers, various measuring instruments, automobile instrument panels, notebook computers, mobile phone handsets, computers, and televisions.

迄今為止，液晶材料已合成出多種化合物，可視其顯示方式或驅動方式及其用途而使用。但，另一方面也對提高液晶顯示元件性能的需求逐年增加，為滿足此需求，需要繼續開發新穎液晶化合物。 To date, liquid crystal materials have been synthesized into a variety of compounds, depending on the mode of display or the manner of driving and their use. However, on the other hand, the demand for improving the performance of liquid crystal display elements has been increasing year by year, and in order to meet this demand, it is necessary to continue to develop novel liquid crystal compounds.

因此，本發明之目的，即在提供一種新穎的含雙環[3.3.0]辛-7-烯結構的液晶化合物。 Accordingly, it is an object of the present invention to provide a novel liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure.

於是，本發明提供一種新穎的含雙環[3.3.0]辛-7-烯結構的液晶化合物，該化合物具有通式(I)所示的結 構： 其中，R1表示1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R1中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連； R2表示-H、-F、-Cl、-CN、-NCS、-SCN、-OCN、-NCO、 或1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R2中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、 -CH=CF-、、-COO-或-OCO-取代，其前提是雜原子 彼此不直接連接； 環A1表示 環A2、A3、和A4相同或不同，各自獨立地表示 的環狀結構； 其中，環A1、A2、A3、和A4代表的環狀結構還可以符合以下a)、b)、c)和d)中的至少一個：a)該環狀結構中的一個或多個氫原子可以被-D、-F、-Cl、-CN、-CF3、-OCF3、-CH2F、-OCH2F、-CF2H、-OCF2H、-OCH3或-CH3取代；b)該環狀結構中一個或多個-CH2-被-O-、-SiH2-、-S-或-CO-取代，其前提是雜原子彼此不直接連接；c)在該環狀結構中，芳環結構中的一個或多個-CH-可以被N取代； d)該環狀結構中一個或多個可以被取代； Z1表示-CF2O-、-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH2CH2CH=CH-、-C2H4OCH2-、-CH2CH=CHCH2-、-CH2CH2CH2O-、-C≡C-或單鍵；Z2、Z3和Z4相同或不同，各自獨立地表示單鍵、-COO-、-CF2O-、-CH2O-、-CH2CH2-、-CF2CH2-、-CF=CF-、-CH=CH-、-CH=CF-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CF2CF2CF2O-、-CH2CH2CF2O-、 -OCF2CF2CF2-、-CH2CF2OCH2-、-CH=CHCF2O-、-CF2OCH=CH-、-CF2OCF=CH-、-CF2OCH=CF-、-CF=CFCF2O-、-CH=CFCF2O-、-CF2OCF=CF-、-CH=CHCH2CH2-、-C2H4OCH2-、-CH2CH=CHCH2-、-OCH2CH2CH2-、-CF=CF-CF=CF-、-C≡C-CF=CF-、-C≡C-CF=CF-C≡C-、-CF=CF-C≡C-CF=CF-、-C≡C-CF2O-或-C≡C-，其中，在該Z2、Z3和Z4的鏈接基團中任意一個-CH2-可被-SiH2-取代；m、n和p相同或不同，各自獨立地表示0、1或2。當m為2，兩個Z2及兩個A2各自為相同或不同；當n為2，兩個Z3及兩個A3各自為相同或不同；當p為2，兩個Z4及兩個A4各自為相同或不同。 Accordingly, the present invention provides a novel liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure having a structure represented by the general formula (I): Wherein R 1 represents a linear or branched alkyl or alkoxy group of 1 to 20 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 1 may be - O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the hetero atom Not directly connected to each other, and the O, S and Si atoms are not directly connected to the ring; R 2 represents -H, -F, -Cl, -CN, -NCS, -SCN, -OCN, -NCO, Or a straight or branched alkyl or alkoxy group having 1 to 20 carbon atoms substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 2 may be -O-, - S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, , -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other; ring A 1 represents Rings A 2 , A 3 , and A 4 are the same or different and each independently represents The cyclic structure represented by the rings A 1 , A 2 , A 3 , and A 4 may also conform to at least one of the following a), b), c), and d): a) the ring One or more hydrogen atoms in the structure may be -D, -F, -Cl, -CN, -CF 3 , -OCF 3 , -CH 2 F, -OCH 2 F, -CF 2 H, -OCF 2 H , -OCH 3 or -CH 3 substituted; b) one or more -CH 2 - in the cyclic structure is substituted by -O-, -SiH 2 -, -S- or -CO-, provided that the heteroatoms are Not directly connected; c) in the cyclic structure, one or more -CH- in the aromatic ring structure may be substituted by N; d) one or more of the cyclic structures Can be Substituted; Z 1 represents -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 ) 4 -, -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -CH 2 CH 2 CH=CH-, -C 2 H 4 OCH 2 -, -CH 2 CH=CHCH 2 -, -CH 2 CH 2 CH 2 O-, -C≡C- or a single bond; Z 2 , Z 3 and Z 4 are the same or different and each independently represents a single bond, -COO-, -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF 2 CH 2 -, -CF=CF-, -CH=CH-, -CH=CF-, -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 - , -OCF 2 CF 2 O -, - CF 2 CF 2 CF 2 O -, - CH 2 CH 2 CF 2 O-, -OCF 2 CF 2 CF 2 -, - CH 2 CF 2 OCH 2 -, - CH = CHCF 2 O-, -CF 2 OCH=CH-, -CF 2 OCF=CH-, -CF 2 OCH=CF-, -CF=CFCF 2 O-, -CH=CFCF 2 O-, -CF 2 OCF= CF-, -CH=CHCH 2 CH 2 -, -C 2 H 4 OCH 2 -, -CH 2 CH=CHCH 2 -, -OCH 2 CH 2 CH 2 -, -CF=CF-CF=CF-, - C≡C-CF=CF-, -C≡C-CF=CF-C≡C-, -CF=CF-C≡C-CF=CF-, -C≡C-CF 2 O- or -C≡ C-, wherein the Z 2, Z 3, and linking group Z 4 is any one of -CH 2 - may be -SiH 2 - substituted; are the same or different m, n and p, each independently represent 0,1 Or 2. When m is 2, two Z 2 and two A 2 are the same or different; when n is 2, two Z 3 and two A 3 are the same or different; when p is 2, two Z 4 and The two A 4 are each the same or different.

本發明的另一目的是提供一種合成該液晶化合物的合成方法。 Another object of the present invention is to provide a method for synthesizing the liquid crystal compound.

本發明的又一目的是提供一種包含該液晶化合物的組合物。 It is still another object of the present invention to provide a composition comprising the liquid crystal compound.

本發明的再一目的是提供一種該液晶組合物在液晶元件中的應用，可應用於含液晶介質的液晶元件，如TN、STN、TFT、VA、ECB、OCB、LCP、PDLC、BiNem、LC LENS、FFS、和IPS等顯示模式的液晶元件。 A further object of the present invention is to provide a liquid crystal composition for use in a liquid crystal cell, which can be applied to a liquid crystal cell containing a liquid crystal medium such as TN, STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC. Display mode liquid crystal elements such as LENS, FFS, and IPS.

本發明通式(I)的含雙環[3.3.0]辛-7-烯結構的液晶化合物具有新穎結構，且具有較低黏度、較大的光學各向異性及較大的介電各向異性。本發明液晶組合物之功效在於使用通式(I)的液晶化合物，而可應用於各種顯示模式 的液晶元件。 The liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure of the formula (I) of the present invention has a novel structure and has a low viscosity, a large optical anisotropy and a large dielectric anisotropy. . The liquid crystal composition of the present invention has the effect of using a liquid crystal compound of the formula (I), and can be applied to various display modes. Liquid crystal element.

以下將就本發明內容進行詳細說明：較佳地，R1表示1-10個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R1中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連； R2表示-H、-F、-Cl、-CN、-NCS、和1-10個碳原子經 至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R2中至少一個-CH2-可以被-O-、-CH=CH-、 -C≡C-、-CF=CF-、-CH=CF-、或-COO-取代，其前提 是雜原子彼此不直接連接。 Hereinafter, the present invention will be described in detail: preferably, R 1 represents a linear or branched alkyl or alkoxy group having 1 to 10 carbon atoms substituted or unsubstituted with at least one halogen, wherein At least one of -CH 2 - in R 1 may be -O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO - or -OCO-substitution, provided that the heteroatoms are not directly connected to each other, and the O, S and Si atoms are not directly bonded to the ring; R 2 represents -H, -F, -Cl, -CN, -NCS, And a linear or branched alkyl or alkoxy group having 1-10 carbon atoms substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 2 may be -O-, - CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, Or -COO-substitution, provided that the heteroatoms are not directly connected to each other.

較佳地，環A1表示 環A2、A3和A4相同或不同，各自獨立地表示 Preferably, ring A 1 represents Rings A 2 , A 3 and A 4 are the same or different and each independently represents

更佳地，環A1表示 環A2、A3和A4相同或不同，各自獨立地表示 More preferably, the ring A 1 represents Rings A 2 , A 3 and A 4 are the same or different and each independently represents

較佳地，Z1表示-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH2CH2CH=CH-、-C2H4OCH2-、-CH2CH2CH2O-、-C≡C-或單鍵； Z2、Z3、和Z4相同或不同，各自獨立地表示-COO-、-CF2O-、-CH2O-、-CH2CH2-、-CF=CF-、-CH=CH-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CH2CH2CF2O-、-CF=CFCF2O-、-C2H4OCH2-、-OCH2CH2CH2-、-C≡C-或單鍵。 Preferably, Z 1 represents -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 ) 4 -, -CH 2 CH 2 CF 2 O -, -CH 2 CF 2 OCH 2 -, -CH 2 CH 2 CH=CH-, -C 2 H 4 OCH 2 -, -CH 2 CH 2 CH 2 O-, -C≡C- or a single bond; Z 2 , Z 3 , and Z 4 are the same or different and each independently represents -COO-, -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF=CF-, -CH=CH- , -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 -, -OCF 2 CF 2 O-, -CH 2 CH 2 CF 2 O-, -CF=CFCF 2 O-, - C 2 H 4 OCH 2 -, -OCH 2 CH 2 CH 2 -, -C≡C- or a single bond.

更佳地，Z1表示-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH2CH2CH=CH-、-C2H4OCH2-、-CH2CH2CH2O-、-C≡C-或單鍵；Z2、Z3、和Z4相同或不同，各自獨立地表示-COO-、-CF2O-、-CH2O-、-CH2CH2-、-CF=CF-、-CH=CH-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CF=CFCF2O-、-C≡C-或單鍵。 More preferably, Z 1 represents -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 ) 4 -, -CH 2 CH 2 CF 2 O -, -CH 2 CF 2 OCH 2 -, -CH 2 CH 2 CH=CH-, -C 2 H 4 OCH 2 -, -CH 2 CH 2 CH 2 O-, -C≡C- or a single bond; Z 2 , Z 3 , and Z 4 are the same or different and each independently represents -COO-, -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF=CF-, -CH=CH- , -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 -, -OCF 2 CF 2 O-, -CF=CFCF 2 O-, -C≡C- or a single bond.

較佳地，m、n和p相同或不同，各自獨立地表示0、1或2，且m+n+p4。 Preferably, m, n and p are the same or different, each independently representing 0, 1 or 2, and m+n+p 4.

較佳地，通式(I)化合物表示 其中，R1表示1-5個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R1中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連；R2表示-H、-F、-CN和1-5個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R2中至少一個-CH2-可以被-O-、-CH=CH-、-C≡C-、 -CF=CF-、-CH=CF-、或-COO-取代，其前提是雜原 子彼此不直接連接；Z1表示-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH2CH2CH2O-、-C≡C-或單鍵；Z2、Z3、和Z4相同或不同，各自獨立地表示-COO-、-CF2O-、-CH2O-、-CH2CH2-、-CF=CF-、-CH=CH-、-C2F4-、-OCF2CF2O-、-CF=CFCF2O-、-C≡C-或單鍵；L1~L4彼此獨立地表示-H、-F或-CH3；L5~L16各自獨立地表示-H、-F、-OCF2H、-CH3、-OCH3、-OCF3或-CF3。 Preferably, the compound of formula (I) is represented Wherein R 1 represents a straight or branched alkyl or alkoxy group of 1 to 5 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 1 may be - O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the hetero atom Not directly connected to each other, and the O, S and Si atoms are not directly bonded to the ring; R 2 represents -H, -F, -CN and a straight or branched chain of 1-5 carbon atoms substituted or unsubstituted by at least one halogen An alkyl or alkoxy group of a chain wherein at least one -CH 2 - in the R 2 may be -O-, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF -, Or -COO-substitution, provided that the heteroatoms are not directly linked to each other; Z 1 represents -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 4 -, -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -CH 2 CH 2 CH 2 O-, -C≡C- or a single bond; Z 2 , Z 3 , and Z 4 identical or different, each independently represents -COO-, -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF=CF-, -CH=CH-, -C 2 F 4 - , -OCF 2 CF 2 O-, -CF=CFCF 2 O-, -C≡C- or a single bond; L 1 ~ L 4 independently of each other represent -H, -F or -CH 3 ; L 5 ~ L 16 Each independently represents -H, -F, -OCF 2 H, -CH 3 , -OCH 3 , -OCF 3 or -CF 3 .

本發明的另一個目的提供一種製備上述液晶化合物的方法，包括如下步驟： Another object of the present invention is to provide a method of preparing the above liquid crystal compound, comprising the steps of:

通式(III-3)化合物主要是通過市售的中間體或者已發表的合成方法合成得到，其中已發表的合成方法包括酯化反應、Wittig反應、碳-碳交叉偶聯反應(Suzuki偶聯、Negishi偶聯、Heck偶聯、Sonogashira偶聯和過渡金屬催化與格氏試劑交叉偶聯反應等)、格氏反應、催化氫化和溴代反應等；或者通過如下路線合成。 The compound of the formula (III-3) is mainly synthesized by a commercially available intermediate or a published synthesis method, and the published synthesis methods include an esterification reaction, a Wittig reaction, and a carbon-carbon cross-coupling reaction (Suzuki coupling). , Negishi coupling, Heck coupling, Sonogashira coupling and transition metal catalysis and Grignard reagent cross-coupling reaction, etc.), Grignard reaction, catalytic hydrogenation and bromination reaction, etc.; or synthesized by the following route.

其中X1是H、F、Cl、Br、I或磺酸酯基等。通式(III)化合物主要是通過市售的中間體或者已發表的合成方法合成得到，其中已發表的合成方法包括酯化反應、Wittig反應、碳-碳交叉偶聯反應(Suzuki偶聯、Negishi偶聯、Heck偶聯、Sonogashira偶聯和過渡金屬催化與格氏試 劑交叉偶聯反應等)、格氏反應、催化氫化和取代反應等。 Wherein X 1 is H, F, Cl, Br, I or a sulfonate group or the like. The compound of the formula (III) is mainly synthesized by a commercially available intermediate or a published synthesis method, wherein the published synthesis methods include an esterification reaction, a Wittig reaction, a carbon-carbon cross-coupling reaction (Suzuki coupling, Negishi). Coupling, Heck coupling, Sonogashira coupling and transition metal catalysis and Grignard reagent cross-coupling reaction, etc.), Grignard reaction, catalytic hydrogenation and substitution reaction.

R5MgX2 (IV)R5為1-9個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R5中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接彼此連接，並且O、S和Si原子不與環直接相連；X2為F、Cl、Br或I；通式(IV)化合物主要是市售的中間體或者已發表的製備格式試劑的經典方法製得。 R 5 MgX 2 (IV)R 5 is a linear or branched alkyl or alkoxy group having 1 to 9 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH in the R 5 2 - may be substituted by -O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-, The premise is that the heteroatoms are not directly connected to each other, and the O, S and Si atoms are not directly connected to the ring; X 2 is F, Cl, Br or I; the compound of the formula (IV) is mainly a commercially available intermediate or Prepared by the classical method of preparing format reagents.

R6為1-8個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R6中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連；X3為Cl、Br或I；通式(V)化合物主要是市售的中間體或者已發表的製備Wittig試劑的前驅物--三苯基膦鹽的經典方法製得。 R 6 is a linear or branched alkyl or alkoxy group of 1-8 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 6 may be -O- , -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the heteroatoms are not Directly linked, and the O, S and Si atoms are not directly attached to the ring; X 3 is Cl, Br or I; the compound of formula (V) is mainly a commercially available intermediate or a published precursor for the preparation of Wittig reagent -- A classical method of triphenylphosphine salt is prepared.

R7-OH (VI)R7為1-8個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R7中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連；主要反應的過程如下： R 7 -OH (VI)R 7 is a straight or branched alkyl or alkoxy group of 1-8 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH in the R 7 2 - may be substituted by -O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-, The premise is that the heteroatoms are not directly connected to each other, and the O, S and Si atoms are not directly connected to the ring; the main reaction process is as follows:

1)丙二酸二乙酯與乙醇鈉反應後，再與通式(III)化合物進行取代反應，得到通式(III-1)化合物；或者丙二酸二乙酯在四氫呋喃溶劑中，氮氣保護下，65至70℃下與通 式(III)化合物進行Suzuki-Miyaura反應，亦可得到通式(III-1)化合物。 1) After reacting diethyl malonate with sodium ethoxide, a substitution reaction with a compound of the formula (III) is carried out to obtain a compound of the formula (III-1); or diethyl malonate in a solvent of tetrahydrofuran, nitrogen protection Under, at 65 to 70 ° C The compound of the formula (III) can be subjected to the Suzuki-Miyaura reaction to give a compound of the formula (III-1).

2)通式(III-1)化合物在無水四氫呋喃中，氮氣保護下，0至10℃的範圍下分批加入四氫鋁鋰，升至室溫(25±3℃)下反應2小時，還原得到通式(III-2)化合物。 2) The compound of the formula (III-1) is added to the tetrahydrogen aluminum lithium in the range of 0 to 10 ° C under anhydrous nitrogen in anhydrous tetrahydrofuran, and the mixture is raised to room temperature (25 ± 3 ° C) for 2 hours to reduce. The compound of the formula (III-2) is obtained.

3)通式(III-2)化合物在二氯甲烷中，在氮氣環境下，0至5℃的範圍下加入2.2當量的溴代試劑，加熱到20至44℃下反應4至24小時，即可得到通式(III-3)化合物；其中溴代試劑包括三溴化磷、三苯基膦+溴素+咪唑或三苯基膦+四溴化碳等。 3) The compound of the formula (III-2) is added to 2.2 equivalents of a bromine reagent in a range of 0 to 5 ° C under a nitrogen atmosphere in dichloromethane, and heated to 20 to 44 ° C for 4 to 24 hours, that is, A compound of the formula (III-3) can be obtained; wherein the bromination reagent includes phosphorus tribromide, triphenylphosphine + bromine + imidazole or triphenylphosphine + carbon tetrabromide and the like.

4)在無水四氫呋喃溶劑中，在氬氣環境下，-80至-75℃的範圍內，將二異丙基胺鋰溶液滴加到丁二酸二甲酯和六甲基次磷醯胺的四氫呋喃溶液中，然後再於-80至-75℃內滴加通式(III-3)化合物的四氫呋喃溶液，加熱至室溫(25±3℃)下反應20小時後，得到通式(III-4)化合物。 4) The lithium diisopropylamide solution is added dropwise to the dimethyl succinate and hexamethylphosphinamide in an anhydrous tetrahydrofuran solvent under an argon atmosphere at a temperature of -80 to -75 °C. In a tetrahydrofuran solution, a tetrahydrofuran solution of the compound of the formula (III-3) is added dropwise at -80 to -75 ° C, and the mixture is heated to room temperature (25 ± 3 ° C) for 20 hours to obtain a formula (III- 4) Compound.

5)在氬氣環境下，-80至-75℃的範圍內，將環己基異丙基胺滴加到1.1當量的正丁基鋰的四氫呋喃溶液中，再滴加0.5當量的通式(III-4)化合物的四氫呋喃溶液中，然後再於-80至-75℃內滴加0.5當量的碘的四氫呋喃溶液，加熱至室溫(25±3℃)後，用稀鹽酸中止反應，得到通式(III-5)化合物。 5) Under an argon atmosphere, in the range of -80 to -75 ° C, cyclohexylisopropylamine is added dropwise to a solution of 1.1 equivalents of n-butyllithium in tetrahydrofuran, and 0.5 equivalent of the formula (III) is added dropwise. -4) A solution of the compound in tetrahydrofuran, followed by dropwise addition of 0.5 equivalent of a solution of iodine in tetrahydrofuran at -80 to -75 ° C, heating to room temperature (25 ± 3 ° C), and then quenching the reaction with dilute hydrochloric acid to give the formula (III-5) compound.

6)通式(III-5)化合物在無水四氫呋喃中，在氮氣環境下，0至-5℃的範圍下分批加入四氫鋁鋰，再於0至-5℃下反應1小時，得到通式(III-6)化合物。 6) The compound of the formula (III-5) is added in an anhydrous tetrahydrofuran under a nitrogen atmosphere at a range of 0 to -5 ° C in portions, and then reacted at 0 to -5 ° C for 1 hour to obtain a pass. a compound of formula (III-6).

7)通式(III-6)化合物、2.2當量的三苯基膦和2.2當量的咪唑在二氯甲烷中，在氮氣環境下，0至5℃的範圍下加入2.2當量的溴，加熱到20至44℃下反應4至24小時，即可得到通式(III-7)化合物。 7) a compound of the formula (III-6), 2.2 equivalents of triphenylphosphine and 2.2 equivalents of imidazole in dichloromethane, under a nitrogen atmosphere, adding 2.2 equivalents of bromine in the range of 0 to 5 ° C, heated to 20 The compound of the formula (III-7) can be obtained by reacting at 44 ° C for 4 to 24 hours.

8)在無水四氫呋喃溶劑中，在氬氣環境下，-80至-75℃的範圍內，將丙二酸二乙酯的四氫呋喃溶液滴加到二異丙 基胺鋰的四氫呋喃溶液中，然後再於-80至-75℃內滴加通式(III-7)化合物的四氫呋喃溶液，升至室溫(25±3℃)下反應20小時後，得到通式(III-8)化合物。 8) A solution of diethyl malonate in tetrahydrofuran is added dropwise to diisopropyl in an anhydrous tetrahydrofuran solvent under an argon atmosphere at a temperature of -80 to -75 °C. The solution of the lithium amide in tetrahydrofuran is then added dropwise to the tetrahydrofuran solution of the compound of the formula (III-7) at -80 to -75 ° C, and the mixture is allowed to react at room temperature (25 ± 3 ° C) for 20 hours to obtain a pass. A compound of formula (III-8).

9)在通式(III-8)化合物、氯化鈉和水在二甲亞碸溶劑中，在氬氣環境下，160至175℃反應6小時，得到通式(III-9)化合物。 9) A compound of the formula (III-9) is obtained by reacting a compound of the formula (III-8), sodium chloride and water in a solvent of dimethyl hydrazine in an argon atmosphere at 160 to 175 ° C for 6 hours.

10)通式(III-9)化合物在無水四氫呋喃中，在氮氣環境下，0至10℃的範圍下分批加入0.5當量的四氫鋁鋰，升至室溫(25±3℃)下反應2小時，還原得到通式(III-10)化合物。 10) The compound of the formula (III-9) is added in a portion of 0 to 10 ° C under a nitrogen atmosphere in an anhydrous atmosphere of 0 to 10 ° C, and 0.5 liter of lithium aluminum hydride is added in portions, and the reaction is carried out at room temperature (25 ± 3 ° C). The compound of the formula (III-10) was obtained by reduction in 2 hours.

11)通式(III-10)化合物和1.2當量的無水吡啶在乾燥二氯甲烷中，在氮氣環境下，0至5℃的範圍下分批加入1.1當量的對甲苯磺醯氯，升至室溫(25±3℃)下反應20小時，得到通式(III-11)化合物。 11) a compound of the formula (III-10) and 1.2 equivalents of anhydrous pyridine are added to dry dichloromethane in a range of 0 to 5 ° C under a nitrogen atmosphere, and 1.1 equivalents of p-toluenesulfonyl chloride are added in portions to the chamber. The reaction was carried out at a temperature of (25 ± 3 ° C) for 20 hours to obtain a compound of the formula (III-11).

12)在氮氣環境下，0至-5℃的範圍下向通式(III-11)化合物的無水四氫呋喃溶液中分批加入2當量的四氫鋁鋰，升至室溫(25±3℃)下反應5小時，得到通式(I-a)化合物。 12) Add 2 equivalents of lithium tetrahydrogenate to a solution of the compound of the formula (III-11) in anhydrous tetrahydrofuran under a nitrogen atmosphere at a temperature of 0 to -5 ° C, and raise to room temperature (25 ± 3 ° C). The reaction was carried out for 5 hours to obtain a compound of the formula (Ia).

13)在氮氣環境下，-75至-70℃的範圍下，將通式(III-10)化合物的二氯甲烷溶液緩緩加入到二乙胺基三氟化硫(DAST)的二氯甲烷溶液中，加完後，自然升至室溫(25±3℃)，得到通式(I-b)化合物。 13) A solution of the compound of the formula (III-10) in methylene chloride is slowly added to the dichloromethane of diethylaminosulfur trifluoride (DAST) under a nitrogen atmosphere at a temperature ranging from -75 to -70 °C. In the solution, after the addition, the temperature was naturally raised to room temperature (25 ± 3 ° C) to obtain a compound of the formula (Ib).

14)在氮氣環境下，-5至0℃的範圍下，在通式(IV)化合物的無水***溶液中緩緩滴加通式(III-11)化合物的四氫呋喃溶液，滴加完後再於-5至0℃下滴加氯化銅鋰的四氫呋喃溶液，滴完後室溫(25±3℃)攪拌20小時，得到通式(I-c)化合物。 14) A solution of the compound of the formula (III-11) in tetrahydrofuran is slowly added dropwise to a solution of the compound of the formula (IV) in anhydrous ether under a nitrogen atmosphere at a range of -5 to 0 ° C. A solution of lithium copper chloride in tetrahydrofuran was added dropwise at -5 to 0 ° C, and the mixture was stirred at room temperature (25 ± 3 ° C) for 20 hours to give a compound of the formula (Ic).

15)20至25℃下，向通式(III-10)化合物的二氯甲烷溶液中分批加入1.5當量的氯鉻酸吡啶鹽(pyridinium chlorochromate，PCC)，加完後再於20至25℃下反應3小時，得到通式(III-12)化合物。 15) Add 1.5 equivalents of pyridinium chlorochromate (PCC) to a solution of the compound of the formula (III-10) in dichloromethane at 20 to 25 ° C, and add 20 to 25 ° C after the addition. The reaction was carried out for 3 hours to obtain a compound of the formula (III-12).

16)-5至0℃的範圍下，在2當量的通式(V)化合物的無水四氫呋喃溶液中加入2.4當量的叔丁醇鉀，加完後在-5至0℃下攪拌0.5小時，然後再於-5至0℃下滴加1當量的通式(III-12)化合物的四氫呋喃溶液，室溫(25±3℃)反應20小時，得到通式(I-d)化合物的順反異構體混合物，通式(I-d)化合物的順反異構體混合物用苯亞磺酸催化下進行順反異構體轉型，再進行結晶純化，可得到純 反式的通式(I-d)化合物。 To a solution of 2 equivalents of the compound of the formula (V) in anhydrous tetrahydrofuran, 2.4 equivalents of potassium t-butoxide are added, and after stirring, the mixture is stirred at -5 to 0 ° C for 0.5 hour, then Further, 1 equivalent of a solution of the compound of the formula (III-12) in tetrahydrofuran is added dropwise at -5 to 0 ° C, and the mixture is reacted at room temperature (25 ± 3 ° C) for 20 hours to obtain a cis-trans isomer of the compound of the formula (Id). a mixture, a cis-trans isomer mixture of a compound of the formula (Id) is subjected to cis-trans isomerization catalyzed by benzenesulfinic acid, and then purified by crystallization to obtain pure A compound of the formula (I-d) in the trans form.

17)將2當量的二氟二溴甲烷溶解在無水四氫呋喃中，在-75至-80℃下，滴加4當量的三(二甲胺基)膦，低溫後保持在-75至-80℃下反應0.5小時，升溫到室溫(25±3℃)，滴加1當量的通式(III-12)化合物的四氫呋喃溶液，滴完後室溫(25±3℃)下反應2小時，得到通式(I-e)化合物。 17) Dissolve 2 equivalents of difluorodibromomethane in anhydrous tetrahydrofuran, add 4 equivalents of tris(dimethylamino)phosphine at -75 to -80 ° C, and keep at -75 to -80 ° C after low temperature. The reaction was carried out for 0.5 hour, and the temperature was raised to room temperature (25±3° C.), and 1 equivalent of a tetrahydrofuran solution of the compound of the formula (III-12) was added dropwise, and the reaction was carried out at room temperature (25±3° C.) for 2 hours after completion of the dropwise addition. a compound of formula (Ie).

18)通式(VI)化合物與氫化鈉在0至50℃下在無水二甲基甲醯胺中反應，得到通式(VI)化合物的鈉鹽，再於30至50℃下滴加通式(III-11)化合物二甲基甲醯胺溶液，在85至90℃下反應6至24小時，即可得到通式(I-f)化合物。 18) A compound of the formula (VI) is reacted with sodium hydride at 0 to 50 ° C in anhydrous dimethylformamide to give a sodium salt of the compound of the formula (VI), and then added dropwise at 30 to 50 ° C. (III-11) A solution of the compound dimethylformamide, which is reacted at 85 to 90 ° C for 6 to 24 hours to obtain a compound of the formula (If).

本發明的又一目的提供一種液晶組合物，包括一種或多種通式(I)所述的液晶化合物。 A further object of the present invention is to provide a liquid crystal composition comprising one or more liquid crystal compounds of the formula (I).

較佳地，該液晶組合物包括一種至五種通式(I)所述的液晶化合物；更佳地，該液晶組合物包含兩種至四種通式(I)所述的液晶化合物。 Preferably, the liquid crystal composition comprises one to five liquid crystal compounds of the formula (I); more preferably, the liquid crystal composition comprises two to four liquid crystal compounds of the formula (I).

根據本發明的液晶組合物，另外的混合組分可以是通常已知的的介晶化合物，即能以純淨態或與其他組分混合地形成液晶相的化合物。一些此類的化合物在例如 DE1804894和CN1158602A中被提及。較佳地，該液晶組合物還包含至少一種通式(Ⅱ)液晶化合物： 其中，R3和R4相同或不同，各自獨立地表示-H、-F、-Cl、-CN、-NCS、-SCN、-OCN、-NCO、-OCHCF2、1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基、或2-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烯基或烯氧基，其中，在該R3和該R4中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、 -CF=CF-、-CH=CF-、、-COO-或-OCO-取代，其前 提是雜原子彼此不直接連接； B1、B2、B3和B4相同或不同，各自獨立地表示 、1,4-伸苯基、2,3-二氟-1,4-伸 苯基、3-氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2-氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、茚滿-2,5-二基、呱啶-1,4-二基、萘-2,6-二基、十氫萘-2,6- 二基或1,2,3,4-四氫萘-2,6-二基，其中該 或中的H可以獨立地被CN或鹵素取代；該 中的一個或兩個不相鄰的-CH2-可以被-O-或-S-取代，該 上任意一個或多個的H可以各自獨立地被F取 代；該中的一個或兩個不相鄰的-CH-可以被N取 代，該上一個或多個中任意的H可以各自獨立地 被F取代；該中的一個或兩個不相鄰的-CH2-可以 被O取代，該上任意的一個或多個H可以各自獨 立地被F取代；Y1、Y2、Y3和Y4相同或不同，各自獨立地表示-OCO-、-COO-、-CF2O-、-CH2O-、-OCH2-、-CH2CH2-、-CF2CH2-、-CF=CF-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-(CH2)3O-、-O(CH2)3-、-COS-、-SCO-、-CH=CF-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CF2CF2CF2O-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH=CHCF2O-、-CF2OCH=CH-、-CF2OCF=CH-、-CF2OCH=CF-、-CF=CFCF2O-、-CF2OCF=CF-、-CH=CHCH2CH2-、-C2H4OCH2-、-CH2CH=CHCH2-、-OCH2CH2CH2-、-CF=CF-CF=CF-、-C≡C-CF=CF-、-C≡C-CF=CF-C≡C-、-CF=CF-C≡C-CF=CF-、-C≡C-CF2O-、-C≡C-或單鍵，其中，在該Y1和Y2中的任意一個-CH2-可被-SiH2-取代；a、b、c和d相同或不同，各自獨立地表示0、1或2。當a為2，兩個B1及Y1各自為相同或不同；當b為2，兩個B2及Y2各自為相同或不同；當c為2，兩個B3及Y3各自為相同或不同；及當d為2，兩個B4及Y4各自為相同或不同。 According to the liquid crystal composition of the present invention, the additional mixed component may be a generally known mesogen compound, that is, a compound which can form a liquid crystal phase in a pure state or in combination with other components. Some such compounds are mentioned, for example, in DE 1804894 and CN1158602A. Preferably, the liquid crystal composition further comprises at least one liquid crystal compound of the formula (II): Wherein R 3 and R 4 are the same or different and each independently represents -H, -F, -Cl, -CN, -NCS, -SCN, -OCN, -NCO, -OCHCF 2 , 1-20 carbon atoms At least one halogen-substituted or unsubstituted linear or branched alkyl or alkoxy group, or a linear or branched alkenyl or olefinic oxygen having 2 to 20 carbon atoms substituted or unsubstituted with at least one halogen a base wherein at least one of -3 - -2 - -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF in R 3 and R 4 -, -CH=CF-, , -COO- or -OCO-substitution, provided that the heteroatoms are not directly connected to each other; B 1 , B 2 , B 3 and B 4 are the same or different and each independently represents , 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-benzene Base, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, indole-2,5 -diyl, acridine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6- Two bases, where or H in can be independently replaced by CN or halogen; One or two non-adjacent -CH 2 - may be replaced by -O- or -S-, Any one or more of H may be independently replaced by F; One or two non-adjacent -CH- in the middle may be replaced by N, Any one of the preceding one or more may be independently replaced by F; One or two non-adjacent -CH 2 - in the middle may be replaced by O, Any one or more of H may be independently substituted by F; Y 1 , Y 2 , Y 3 and Y 4 are the same or different and each independently represents -OCO-, -COO-, -CF 2 O-, - CH 2 O-, -OCH 2 -, -CH 2 CH 2 -, -CF 2 CH 2 -, -CF=CF-, -CH=CH-, -CH(CH 3 )CH 2 -, -CH 2 CH (CH 3 )-, -(CH 2 ) 3 O-, -O(CH 2 ) 3 -, -COS-, -SCO-, -CH=CF-, -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 -, -OCF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -CH= CHCF 2 O-, -CF 2 OCH=CH-, -CF 2 OCF=CH-, -CF 2 OCH=CF-, -CF=CFCF 2 O-, -CF 2 OCF=CF-, -CH=CHCH 2 CH 2 -, -C 2 H 4 OCH 2 -, -CH 2 CH=CHCH 2 -, -OCH 2 CH 2 CH 2 -, -CF=CF-CF=CF-, -C≡C-CF=CF- , -C≡C-CF=CF-C≡C-, -CF=CF-C≡C-CF=CF-, -C≡C-CF 2 O-, -C≡C- or a single bond, wherein Any one of Y 1 and Y 2 -CH 2 - may be substituted by -SiH 2 -; a, b, c and d are the same or different and each independently represents 0, 1 or 2. When a is 2, two B 1 and Y 1 are the same or different; when b is 2, two B 2 and Y 2 are the same or different; when c is 2, two B 3 and Y 3 are each The same or different; and when d is 2, the two B 4 and Y 4 are the same or different.

該通式(Ⅱ)液晶化合物表示 The liquid crystal compound of the formula (II) is represented by

較佳地，以該液晶組合物的總重量為100wt%， 該通式(I)化合物的用量範圍為5至50wt%，及該通式(Ⅱ)化合物的用量範圍為50至95wt%；更佳地，該通式(I)化合物的用量範圍為10至30wt%，及該通式(Ⅱ)化合物的用量範圍為70至90wt%。 Preferably, the total weight of the liquid crystal composition is 100% by weight, The compound of the formula (I) is used in an amount ranging from 5 to 50% by weight, and the compound of the formula (II) is used in an amount ranging from 50 to 95% by weight; more preferably, the compound of the formula (I) is used in an amount ranging from 10 to 10 30 wt%, and the compound of the formula (II) is used in an amount ranging from 70 to 90% by weight.

本發明的再一目的是提供一種新穎的含雙環[3.3.0]辛-7-烯結構的液晶化合物，其適合作為液晶介質的組成，並可應用於含液晶介質的液晶元件，如TN、STN、TFT、VA、ECB、OCB、LCP、PDLC、BiNem、LC LENS、FFS、和IPS等顯示模式的液晶元件。 A further object of the present invention is to provide a novel liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure which is suitable as a composition of a liquid crystal medium and can be applied to a liquid crystal element containing a liquid crystal medium such as TN, Display mode liquid crystal elements such as STN, TFT, VA, ECB, OCB, LCP, PDLC, BiNem, LC LENS, FFS, and IPS.

本發明提供的新穎的含雙環[3.3.0]辛-7-烯結構的液晶化合物具有良好的化學和物理性質，比其他相應液晶材料具有較低的黏度，較大的光學各向異性和較大的介電各向異性。 The novel liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure provided by the invention has good chemical and physical properties, has lower viscosity than other corresponding liquid crystal materials, and has larger optical anisotropy and Large dielectric anisotropy.

實施例 Example

以下將結合具體實施例來說明本發明。需要說明的是，下面的實施例為本發明的示例，僅用來說明本發明，而不用來限制本發明。在不偏離本發明主旨或範圍的情況下，可進行本發明構思內的其他組合和各種改良。 The invention will now be described in connection with specific embodiments. It is to be understood that the following examples are illustrative of the invention and are not intended to limit the invention. Other combinations and various modifications within the inventive concept can be made without departing from the spirit or scope of the invention.

為便於表達，以下各實施例中，液晶化合物的基團結構用表1所列的代碼表示： For ease of expression, in the following examples, the group structure of the liquid crystal compound is represented by the codes listed in Table 1:

以如下結構式的化合物為例： 該結構式如用表1所列代碼表示，則可表達為：3PUQUF，代碼中的Q代表二氟伸甲基氧基；代碼中的C代表伸環己烷基；代碼中的U代表2,6-二氟-1,4-伸苯基。 Take a compound of the following structural formula as an example: The structural formula is expressed by the code listed in Table 1, and can be expressed as: 3PUQUF, where Q represents difluoromethyloxy; in the code, C represents a cyclohexane group; U in the code represents 2, 6-Difluoro-1,4-phenylene.

實施例1Example 1

製備的化合物HCLC-06的合成方法如下所示： The synthesis method of the prepared compound HCLC- 06 is as follows:

HCLC-06-12參考文獻EP1160251合成 HCLC -06-12 reference EP1160251 synthesis

其具體合成步驟如下： The specific synthesis steps are as follows:

1)HCLC-06-11的合成 1) Synthesis of HCLC -06-11

氮氣保護下向10L三頸瓶中加入307g丙二酸二乙酯、5L無水四氫呋喃、459g HCLC-06-12、18.4g Pd(dba)2(雙(二伸苄基丙酮)鈀)、12.9g P(t-Bu)3和800g K3PO4，65至70℃下反應8小時，反應液轉入5L單口瓶中旋轉濃縮，得到粗產物，加入4L二氯甲烷溶解，過濾，有機相用1L 1M稀鹽酸洗滌，再用1L飽和碳酸氫鈉溶液洗滌，二氯甲烷溶液乾燥濃縮，得到棕黃色油狀物625g，用PE：EA=8：1沖提液進行管柱層析，將層析液合併，用旋轉濃縮儀減壓濃縮溶劑，得到497.5g淺黃色油狀物(HCLC-06-11)，純度：97.6%，產率：85%。 Under a nitrogen atmosphere, a 307 g of diethyl malonate, 5 L of anhydrous tetrahydrofuran, 459 g of HCLC-06-12, 18.4 g of Pd(dba) 2 (bis(di-benzylideneacetone)palladium), 12.9 g were placed in a 10 L three-necked flask. P(t-Bu) 3 and 800g K 3 PO 4 , reacted at 65 to 70 ° C for 8 hours, and the reaction solution was transferred to a 5 L single-mouth bottle and concentrated by rotation to obtain a crude product, dissolved in 4 L of dichloromethane, filtered, and used for organic phase. Washed with 1 L of 1M diluted hydrochloric acid, washed with 1 L of saturated sodium bicarbonate solution, and dried and concentrated with methylene chloride to give 625 g of brownish oil, and the column was chromatographed with PE:EA=8:1 The liquid was combined and concentrated under reduced pressure using a rotary concentrator to afford 497.5 g of pale yellow oil ( HCLC -06-11 ), purity: 97.6%, yield: 85%.

2)HCLC-06-10的合成 2) Synthesis of HCLC -06-10

497.5g HCLC-06-11溶解在無水四氫呋喃中，在氮氣環境下，0至5℃的範圍下分批加入133g四氫鋁鋰，升至室溫(25±3℃)下反應6小時，緩緩滴加100g乙酸乙酯，再滴加140g水，過濾除去偏鋁酸鹽，濾液旋轉濃縮得到379g淺黃色油狀物，用PE：EA=1：1沖提液進行管柱層析，再用乙酸乙酯沖提，將TLC無雜點的層析液合併，用旋轉濃縮儀減壓濃縮溶劑得到350.5g無色透明液體(HCLC-06-10)，純度：98.7%，產率：92.1%。 497.5 g of HCLC -06-11 was dissolved in anhydrous tetrahydrofuran, and 133 g of lithium tetrahydrogenate was added in portions under a nitrogen atmosphere at a range of 0 to 5 ° C, and the reaction was carried out at room temperature (25 ± 3 ° C) for 6 hours. 100 g of ethyl acetate was added dropwise, and 140 g of water was added dropwise, and the metaaluminate was removed by filtration. The filtrate was concentrated by spin to obtain 379 g of a pale yellow oil, and subjected to column chromatography using a PE:EA=1:1 extract. The mixture was extracted with ethyl acetate, and the TLC-free chromatographic solution was combined. The solvent was concentrated under reduced pressure using a rotary concentrator to obtain 350.5 g of a colorless transparent liquid ( HCLC -06-10), purity: 98.7%, yield: 92.1% .

3)HCLC-06-09的合成 3) Synthesis of HCLC-06-09

10L三頸瓶中加入350.5g HCLC-06-10，4L三氯甲烷，安裝乾燥、迴流和尾氣吸收裝置，攪拌下0至5℃滴加739g三溴化磷的500mL三氯甲烷溶液，滴完後，室溫(25±3℃)攪拌30分鐘，再迴流反應6小時，TLC監控，待反應完全，停止加熱，自然冷卻至室溫(25±3℃)，將反應液緩緩加入到4L飽和磷酸鈉的冰水溶液中，然後再用1M(mol/L)的氫氧化鈉溶液調節pH至14，轉入分液漏斗中分液，水層用500mL三氯甲烷萃取三次，有機體層合併用飽和碳酸氫鈉水溶液洗滌兩次，有機層再用120g無水硫酸鈉乾燥，再用旋轉濃縮儀濃縮溶劑，得到592.5g棕淡黃色油狀物。粗產物用石油醚進行管柱層析，將層析液合併，用旋轉濃縮儀減壓濃縮溶劑，得到460g白色固體(HCLC-06-09)，純度：96.7%，產率：90.5%。 Add 100.5g of HCLC -06-10, 4L of chloroform to a 10L three-necked flask, install a dry, reflux and tail gas absorption device, add 739g of phosphorus tribromide in 500mL of chloroform solution at 0 to 5 °C with stirring. After that, the mixture was stirred at room temperature (25±3° C.) for 30 minutes, and refluxed for 6 hours. TLC was monitored, the reaction was completed, the heating was stopped, and the mixture was naturally cooled to room temperature (25±3° C.), and the reaction liquid was slowly added to 4 L. Saturated sodium phosphate in ice water solution, and then adjusted to pH 14 with 1M (mol / L) sodium hydroxide solution, transferred to a separatory funnel, and the aqueous layer was extracted three times with 500 mL of chloroform, and the organic layer was combined. The organic layer was washed twice with saturated aqueous sodium hydrogen sulfate and dried over anhydrous sodium sulfate. The crude product was subjected to column chromatography using petroleum ether, and the solvent was combined, and the solvent was concentrated under reduced pressure to give 460 g of white solid ( HCLC -06-09), purity: 96.7%, yield: 90.5%.

4)HCLC-06-08的合成 4) Synthesis of HCLC -06-08

10L三頸瓶中加入162g丁二酸二甲酯，3L無水四氫呋喃，270mL六甲基次磷醯胺，氬氣保護下降溫至-75℃，滴加1L 1M的二異丙基胺鋰溶液，滴完後-80至-75℃攪拌45分鐘，再於-80至-75℃下滴加460g HCLC-06-09的500mL無水四氫呋喃溶液，滴加完畢，-80至-75℃攪拌2小時，再自然升溫至室溫(25±3℃)反應20小時；將反應液倒入500mL飽和氯化銨水溶液中，轉入分液漏斗中分液，水層用300mL乙酸乙酯萃取三次，有機體層合併用飽和碳酸氫鈉水溶液洗滌兩次，有機層再用100g無水硫酸鈉乾燥，再用旋轉濃縮儀濃縮溶劑，得到260g棕黃色固體。粗產物用PE：EA=5：1沖提液進行管柱層析，將無雜點的層析液合併，用旋轉濃縮儀減壓濃縮溶劑，得到184.5g淡黃色固體(HCLC-06-08)，純度：94.7%，產率：76%。 In a 10 L three-necked flask, 162 g of dimethyl succinate, 3 L of anhydrous tetrahydrofuran, 270 mL of hexamethylphosphiniumamine, argon gas protection and the temperature was lowered to -75 ° C, and 1 L of 1 M lithium diisopropylamide solution was added dropwise. After the completion of the dropwise addition, the mixture was stirred at -80 to -75 ° C for 45 minutes, and then 460 g of a solution of HCLC- 06-09 in 500 mL of anhydrous tetrahydrofuran was added dropwise at -80 to -75 ° C, and the mixture was added dropwise, and the mixture was stirred at -80 to -75 ° C for 2 hours. The mixture was naturally warmed to room temperature (25 ± 3 ° C) for 20 hours; the reaction solution was poured into 500 mL of saturated aqueous ammonium chloride solution, transferred to a separating funnel, and the aqueous layer was extracted three times with 300 mL of ethyl acetate. The mixture was washed twice with aq. aq. sodium hydrogen sulfate, and then evaporated and evaporated. The crude product was subjected to column chromatography using a PE:EA=5:1 extract, and the chromatographic solution was combined, and the solvent was concentrated under reduced pressure using a rotary concentrator to obtain 184.5 g of pale yellow solid ( HCLC -06-08) ), purity: 94.7%, yield: 76%.

5)HCLC-06-07的合成 5) Synthesis of HCLC -06-07

在氬氣環境下，-80至-75℃的範圍內，將145g環己基異丙基胺滴加到415mL 2.5M正丁基鋰的300mL四氫呋喃溶液中，保溫攪拌0.5小時，再滴加184.5g HCLC-06-08的300mL四氫呋喃溶液中，然後再於-80至-75℃內滴加119.5g的碘的300mL四氫呋喃溶液，滴完後，自然升至室溫(25±3℃)後，滴加400mL 2M稀鹽酸，再加入400mL乙酸乙酯和300mL飽和氯化鈉溶液，攪拌15分鐘，分液，水層用300mL乙酸乙酯萃取三次，有機體層合併用飽和碳酸氫鈉水溶液洗滌兩次，有機層再用100g無水硫酸鈉乾燥，再用旋轉濃縮儀濃縮溶劑，得到176g淡黃色液體。 粗產物用250mL無水乙醇再結晶兩次，得到白色粉末狀固體HCLC-06-07 120g，純度：98.9%，產率：65.4%。 Under an argon atmosphere, 145 g of cyclohexylisopropylamine was added dropwise to a solution of 415 mL of 2.5 M n-butyllithium in 300 mL of tetrahydrofuran under an argon atmosphere, and the mixture was stirred for 0.5 hour while adding 184.5 g. In a solution of HCLC -06-08 in 300 mL of tetrahydrofuran, then add 119.5 g of iodine in 300 mL of tetrahydrofuran solution at -80 to -75 ° C. After the dropwise addition, naturally rise to room temperature (25 ± 3 ° C), and then drip. 400 mL of 2M dilute hydrochloric acid was added, 400 mL of ethyl acetate and 300 mL of saturated sodium chloride solution were added, and the mixture was stirred for 15 minutes, and the aqueous layer was extracted with 300 mL of ethyl acetate. The organic layer was combined and washed twice with saturated aqueous sodium hydrogen carbonate. The organic layer was dried over anhydrous sodium sulfate (100 g), and then evaporated. The crude product was recrystallized twice from 250 mL of dry ethanol to afford white powdery solid HCLC -06-07 120 g, purity: 98.9%, yield: 65.4%.

6)HCLC-06-06的合成 6) Synthesis of HCLC-06-06

120g HCLC-06-07溶解在800mL無水四氫呋喃中，氮氣保護下，0至-5℃的範圍下分批加入29g四氫鋁鋰，再於0至-5℃下反應1小時，充分攪拌下緩緩滴加20g乙酸乙酯，再滴加30g水，過濾除去偏鋁酸鹽，濾液旋轉濃縮得到379g淺黃色油狀物，用PE：EA=1：1沖提液進行管柱層析，再用乙酸乙酯沖提，將無雜點的層析液合併，用旋轉濃縮儀減壓濃縮溶劑得到94.5g白色固體，再用25mL乙酸乙酯和100mL石油醚再結晶兩次，得到66g白色固體(HCLC-06-06)，純度：99.3%，產率：64.4%。 120g of HCLC -06-07 was dissolved in 800 mL of anhydrous tetrahydrofuran. Under nitrogen protection, 29 g of lithium tetrahydroaluminum was added in portions ranging from 0 to -5 ° C, and then reacted at 0 to -5 ° C for 1 hour, stirring well. 20 g of ethyl acetate was added dropwise, 30 g of water was added dropwise, and the metaaluminate was removed by filtration. The filtrate was concentrated by rotation to obtain 379 g of a pale yellow oil, which was subjected to column chromatography using a PE:EA=1:1 extract. The mixture was extracted with ethyl acetate, and the residue-free chromatography was combined, and the solvent was concentrated under reduced pressure to give 94.5 g of white solid, and then recrystallized twice with 25 mL of ethyl acetate and 100 mL of petroleum ether to give 66 g of white solid. ( HCLC- 06-06), purity: 99.3%, yield: 64.4%.

7)HCLC-06-05的合成 7) Synthesis of HCLC-06-05

66g化合物HCLC-06-06、114g三苯基膦和29.5g咪唑溶解在600mL乾燥二氯甲烷中，在氮氣環境下，0至5℃的範圍下加69.5g溴素的150mL二氯甲烷溶液，升至30℃下反應4小時，反應液倒入300mL飽和碳酸氫鈉溶液中，分液，有機相用300mL去離子水洗滌兩次，乾燥，旋轉濃縮，粗產物再用石油醚沖提進行管柱層析，濃縮得到71g白色固體HCLC-06-05，純度：98.7%，產率：78.5%。 66 g of compound HCLC-06-06, 114 g of triphenylphosphine and 29.5 g of imidazole were dissolved in 600 mL of dry dichloromethane, and a solution of 69.5 g of bromine in 150 mL of dichloromethane was added under a nitrogen atmosphere at a temperature of 0 to 5 °C. Raise to 30 ° C for 4 hours, the reaction solution is poured into 300 mL of saturated sodium bicarbonate solution, liquid separation, the organic phase is washed twice with 300 mL of deionized water, dried, concentrated by rotation, and the crude product is then extracted with petroleum ether. Column chromatography and concentration gave 71 g of white solid HCLC -06-05, purity: 98.7%, yield: 78.5%.

8)HCLC-06-04的合成 8) Synthesis of HCLC-06-04

在無水四氫呋喃溶劑中，在氬氣環境下，-80至-75℃的範圍內，將含25g丙二酸二乙酯的100mL四氫呋喃溶液滴加到345mL 1M二異丙基胺鋰的四氫呋喃溶液中，然 後再於-80至-75℃內滴加71g化合物HCLC-06-05的150mL四氫呋喃溶液，升至室溫(25±3℃)下反應20小時後，加入400mL飽和氯化銨溶液，分液，水層用300mL乙酸乙酯萃取三次，有機體層合併用飽和氯化鈉水溶液洗滌兩次，80g無水硫酸鈉乾燥，再用旋轉濃縮儀濃縮溶劑，得到82.5g淡黃色液體。粗產物用PE：EA=6：1沖提液進行管柱層析，合併無雜點的層析液，用旋轉濃縮儀減壓濃縮溶劑，得到52.5g淡黃色液體HCLC-06-04，純度：98.7%，產率：74.4%。 In a solvent of anhydrous tetrahydrofuran, a solution of 25 g of diethyl malonate in 100 mL of tetrahydrofuran was added dropwise to a solution of 345 mL of 1 M lithium diisopropylamide in tetrahydrofuran under an argon atmosphere at a temperature of -80 to -75 °C. Then, a solution of 71 g of compound HCLC-06-05 in 150 mL of tetrahydrofuran was added dropwise at -80 to -75 ° C, and the mixture was allowed to react at room temperature (25 ± 3 ° C) for 20 hours, and then 400 mL of a saturated ammonium chloride solution was added thereto. The aqueous layer was extracted three times with 300 mL of ethyl acetate. The organic layer was combined and washed twice with saturated aqueous sodium chloride, and dried over anhydrous sodium sulfate. The crude product was subjected to column chromatography with PE:EA=6:1 extract, and the chromatographic solution was combined with a non- doped point. The solvent was concentrated under reduced pressure with a rotary concentrator to obtain 52.5 g of pale yellow liquid HCLC -06-04, purity. : 98.7%, yield: 74.4%.

9)HCLC-06-03的合成 9) Synthesis of HCLC -06-03

在52.5g化合物HCLC-06-04、53.5g氯化鈉和40g水在400mL二甲亞碸溶劑中，在氬氣環境下，迴流反應6小時，反應完畢，在氬氣環境下油浴80至90℃減壓蒸乾溶劑，粗產物加入100mL甲苯和50mL水，分液水洗，有機相用旋轉濃縮儀濃縮溶劑，得到46g淡黃色液體，粗產物用PE：EA=8：1沖提液進行管柱層析，合併無雜點的層析液，用旋轉濃縮儀減壓濃縮溶劑，得到31.5g淡黃色液體HCLC-06-03，純度：97.6%(順反異構體1：1)，產率：71.3%。 52.5g of compound HCLC -06-04, 53.5g of sodium chloride and 40g of water in 400mL of dimethyl hydrazine solvent, under argon atmosphere, reflux reaction for 6 hours, the reaction is completed, in an argon atmosphere oil bath 80 to The solvent was evaporated to dryness under reduced pressure at 90 ° C, and the crude product was added to 100 mL of toluene and 50 mL of water, and the mixture was washed with water, and the organic phase was concentrated with a rotary concentrator to obtain 46 g of pale yellow liquid, and the crude product was subjected to PE:EA=8:1 extract. Column chromatography, combining the chromatographic solution without impurities, and concentrating the solvent under reduced pressure with a rotary concentrator to obtain 31.5 g of pale yellow liquid HCLC -06-03, purity: 97.6% (cis-trans isomer 1:1), Yield: 71.3%.

10)HCLC-06-02的合成 10) Synthesis of HCLC -06-02

31.5g化合物HCLC-06-03在250mL無水四氫呋喃中，在氮氣環境下，0至10℃的範圍下分批加入3g的四氫鋁鋰，升至室溫(25±3℃)下反應12小時，緩慢加入十水硫酸鈉破壞過量的四氫鋁鋰，待反應系統中固體變為黃白色後停 止加十水硫酸鈉。減壓過濾，濾餅用150mL乙酸乙酯洗滌3次，合併有機相，濃縮得到29g粗產物，粗產物用PE：EA=1：1沖提液進行管柱層析，再用乙酸乙酯沖提，將TLC無雜點的層析液合併，用旋轉濃縮儀減壓濃縮溶劑得到27g白色固體，再用20mL石油醚和3mL乙醇再結晶三次，得到7.5g白色固體HCLC-06-02，純度：97.4%，產率：26.8%。 31.5 g of compound HCLC -06-03 In 250 mL of anhydrous tetrahydrofuran, 3 g of lithium tetrahydrogenate was added in portions under a nitrogen atmosphere at a range of 0 to 10 ° C, and the reaction was carried out at room temperature (25 ± 3 ° C) for 12 hours. Slowly add sodium sulfate decahydrate to destroy excess lithium aluminum hydride. After the solid in the reaction system turns yellowish white, stop adding sodium sulfate decahydrate. Filtration under reduced pressure, the filter cake was washed three times with 150 mL of ethyl acetate. The organic phase was combined and concentrated to give 29 g of crude product. The crude product was subjected to column chromatography with PE:EA=1:1 extract, and then washed with ethyl acetate. The TLC impurity-free chromatography liquid was combined, and the solvent was concentrated under reduced pressure with a rotary concentrator to obtain 27 g of a white solid, which was recrystallized three times with 20 mL of petroleum ether and 3 mL of ethanol to obtain 7.5 g of white solid HCLC -06-02, purity. : 97.4%, yield: 26.8%.

11)HCLC-06-01的合成 11) Synthesis of HCLC -06-01

2.5g化合物HCLC-06-02和0.7g無水吡啶在20mL乾燥二氯甲烷中，在氮氣環境下，0至5℃的範圍下加入1.7g對甲苯磺醯氯，升至室溫(25±3℃)下反應20小時，反應液水洗，濃縮得到3.9g淺黃色固體，粗產物用15mL乙醇和2mL乙酸乙酯再結晶兩次，得到白色固體HCLC-06-01 3.2g，HPLC：99.6%，產率：88.9%。 2.5 g of compound HCLC -06-02 and 0.7 g of anhydrous pyridine were added to 1.7 g of p-toluenesulfonyl chloride in a range of 0 to 5 ° C under nitrogen atmosphere in 20 mL of dry dichloromethane, and raised to room temperature (25 ± 3). The reaction was carried out for 20 hours at ° C., and the reaction mixture was washed with water and evaporated to give 3.9 g of pale yellow solid. The crude product was recrystallized twice with 15 mL of ethanol and 2 mL of ethyl acetate to afford white solid HCLC -06-01 3.2 g, HPLC: 99. Yield: 88.9%.

12)HCLC-06的合成 12) Synthesis of HCLC- 06

在氮氣環境下，-5至0℃的範圍下，於3.2g化合物HCLC-06-01的50mL無水***溶液中緩緩滴加市售的19mL 1M(mol/L)乙基溴化鎂四氫呋喃溶液，滴加完後再於-5至0℃下滴加2mL 1M新製的氯化銅鋰四氫呋喃溶液，滴完後室溫(25±3℃)攪拌20小時，加入20mL飽和氯化銨溶液攪拌，分液，水相用20mL***萃取兩次，有機相合併濃縮得到1.82g淺黃色固體，粗產物再用石油醚進行管柱層析，得到1.72g白色固體，再用5mL乙醇再結晶兩次，得到化合物HCLC-06 1.34g，純度：99.8%，產率： 75.3%。 Under a nitrogen atmosphere, in a range of -5 to 0 ° C, a commercially available 19 mL of 1 M (mol/L) ethylmagnesium bromide tetrahydrofuran solution was slowly added dropwise to 3.2 g of compound HCLC- 06-01 in 50 mL of anhydrous ether. After the dropwise addition, 2 mL of 1M fresh copper chloride tetrahydrofuran solution was added dropwise at -5 to 0 ° C. After the completion of the dropwise addition, the mixture was stirred at room temperature (25 ± 3 ° C) for 20 hours, and stirred with 20 mL of a saturated ammonium chloride solution. The liquid phase was extracted twice with 20 mL of diethyl ether. The organic phase was combined and concentrated to give a pale yellow solid. The crude product was subjected to column chromatography with petroleum ether to give 1.72 g of white solid. The compound HCLC -06 1.34 g was obtained, purity: 99.8%, yield: 75.3%.

GC-MS：EI離子源m/z：356.3。 GC-MS: EI ion source m/z: 356.3.

1H NMR(300MHz,CDCl3),δ(ppm)：7.78-7.42(m,4H),7.31-7.23(m,2H),3.58-3.30(m,1H),2.76-2.49(m,4H),2.44-2.16(m,2H),2.09-1.75(m,3H),1.70-1.42(m,2H),1.33-1.17(m,2H),0.89(t,J=13.0Hz,3H)。 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.78-7.42 (m, 4H), 7.31-7.23 (m, 2H), 3.58-3.30 (m, 1H), 2.76-2.49 (m, 4H) , 2.44-2.16 (m, 2H), 2.09-1.75 (m, 3H), 1.70-1.42 (m, 2H), 1.33-1.17 (m, 2H), 0.89 (t, J = 13.0Hz, 3H).

實施例2Example 2

製備的化合物HCLC-06A的合成方法如下所示： The synthesis method of the prepared compound HCLC-06A is as follows:

在氮氣環境下，0至-5℃的範圍下向1g化合物HCLC-06-01的20mL無水四氫呋喃溶液中加入0.15g四氫鋁鋰，升至室溫(25±3℃)下反應5小時，緩慢加入十水硫酸鈉破壞過量的四氫鋁鋰，待反應系統中固體變為黃白色後停止加十水硫酸鈉。減壓過濾，濾餅用10mL乙酸乙酯洗滌3次，合併有機相，濃縮得29g粗產物，粗產物用石油醚進行管柱層析，得到0.48g白色固體，HCLC-06A，純度：99.7%，產率：72.9%。 To a solution of 1 g of compound HCLC- 06-01 in 20 mL of anhydrous tetrahydrofuran under a nitrogen atmosphere at a temperature of 0 to -5 ° C, 0.15 g of lithium aluminum hydride was added, and the mixture was allowed to react at room temperature (25 ± 3 ° C) for 5 hours. Slowly add sodium sulfate decahydrate to destroy excess lithium aluminum hydride. After the solid in the reaction system turns yellowish white, stop adding sodium sulfate decahydrate. Filtration under reduced pressure, the filter cake was washed three times with 10 mL of ethyl acetate. The organic phase was combined and concentrated to give 29 g of crude product. The crude product was subjected to column chromatography with petroleum ether to give 0.48 g of white solid, HCLC -06A, purity: 99.7% , Yield: 72.9%.

GC-MS：EI離子源m/z：328.2。 GC-MS: EI ion source m/z: 328.2.

1H NMR(300MHz,CDCl3),δ(ppm)：7.78-7.42(m,4H),7.31-7.23(m,2H),3.58-3.30(m,1H),2.76-2.49(m,4H),2.44-2.16(m,2H),2.09-1.75(m,3H),0.86(d,J=6.8Hz,3H)。 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.78-7.42 (m, 4H), 7.31-7.23 (m, 2H), 3.58-3.30 (m, 1H), 2.76-2.49 (m, 4H) , 2.44 - 2.16 (m, 2H), 2.09 - 1.75 (m, 3H), 0.86 (d, J = 6.8 Hz, 3H).

實施例3Example 3

製備的化合物HCLC-06B的合成方法如下所示： The synthesis method of the prepared compound HCLC- 06B is as follows:

氮氣保護下，-75至-70℃的範圍下，將1g化合物HCLC-06-02的10mL二氯甲烷溶液緩緩加入到0.7g二乙胺基三氟化硫(DAST)的20mL二氯甲烷溶液中，加完後，自然升至室溫(25±3℃)，加入10mL飽和氯化銨溶液，分液，有機相用10mL飽和碳酸氫鈉溶液洗滌兩次，乾燥，濃縮得到0.9g白色固體，粗產物用2mL乙醇再結晶兩次，得到0.65g白色固體，HCLC-06B，純度：99.6%，產率：65%。 Under nitrogen protection, 1 g of compound HCLC- 06-02 in 10 mL of dichloromethane was slowly added to 0.7 g of diethylaminosulfur trifluoride (DAST) in 20 mL of dichloromethane at a temperature of -75 to -70 °C. In the solution, after the addition, naturally rise to room temperature (25 ± 3 ° C), add 10mL saturated ammonium chloride solution, separate the liquid, the organic phase is washed twice with 10mL saturated sodium bicarbonate solution, dried, concentrated to give 0.9g white The solid crude product was recrystallized twice with 2mL of ethanol, to give 0.65g of white solid, HCLC -06B, purity: 99.6%, yield: 65%.

GC-MS：EI離子源m/z：346.2。 GC-MS: EI ion source m/z: 346.2.

實施例4Example 4

製備的化合物HCLC-06C的合成方法如下所示： The synthesis method of the prepared compound HCLC- 06C is as follows:

1)HCLC-06C-01的合成 1) Synthesis of HCLC-06C-01

20至25℃下，於4g化合物HCLC-06-02的50二氯甲烷溶液中分批加入3.7g的PCC，加完後再於20至25℃下反應3小時，反應液進行管柱層析，濃縮得到4.1g，粗產物用10mL異丙醇再結晶兩次，得到3.2g白色固體HCLC-06C-01，純度：97.4%，產率：80.5%。 3.7 g of PCC was added in portions to 4 g of compound HCLC- 06-06 in 50 methylene chloride at 20 to 25 ° C. After the addition, the reaction was carried out at 20 to 25 ° C for 3 hours, and the reaction solution was subjected to column chromatography. Concentration gave 4.1 g, and the crude product was recrystallized twice from 10 mL of isopropyl alcohol to give 3.2 g of white solid HCLC -06 C </ RTI></RTI></RTI> purity: 97.4%, yield: 80.5%.

2)HCLC-06C的合成 2) Synthesis of HCLC-06C

-5至0℃的範圍下，於4.3g溴乙烷三苯基膦鹽的50mL無水四氫呋喃溶液中加入1.56g叔丁醇鉀，加完後在-5 至0℃下攪拌0.5小時，然後再於-5至0℃下滴加2g化合物HCLC-06C-01的20mL四氫呋喃溶液，滴完後，室溫(25±3℃)反應20小時，反應液濃縮，以石油醚沖提進行管柱層析，濃縮得到1.9g淺黃色油狀物；粗產物加入到10mL石油醚中，在氮氣環境下加入0.3g苯亞磺酸鈉和2mL 1M稀鹽酸，水浴60℃反應3小時，加入5mL飽和碳酸鈉溶液和20mL石油醚，分液，有機相再用20mL水洗滌兩次，有機相乾燥，進行管柱層析，濃縮得到1.6g粗產物，再用5mL乙醇再結晶三次，得到0.6g白色固體HCLC-06C，純度：99.8%，產率：29%。 To a solution of 4.3 g of triethylphosphonium bromide in 50 mL of anhydrous tetrahydrofuran, 1.56 g of potassium t-butoxide was added at a temperature of -5 to 0 ° C. After the addition, the mixture was stirred at -5 to 0 ° C for 0.5 hour, and then 2 g of compound HCLC- 06C-01 in 20 mL of tetrahydrofuran solution was added dropwise at -5 to 0 ° C. After the completion of the dropwise addition, the reaction was carried out at room temperature (25 ± 3 ° C) for 20 hours, and the reaction liquid was concentrated, and the column was layered with petroleum ether. It was concentrated and concentrated to obtain 1.9 g of a pale yellow oil; the crude product was added to 10 mL of petroleum ether, and 0.3 g of sodium benzenesulfinate and 2 mL of 1 M diluted hydrochloric acid were added under a nitrogen atmosphere, and the mixture was reacted at 60 ° C for 3 hours in a water bath, and 5 mL of saturated carbonic acid was added thereto. The sodium solution and 20 mL of petroleum ether were separated, and the organic phase was washed twice with 20 mL of water. The organic phase was dried, and then subjected to column chromatography, and concentrated to give 1.6 g of crude product, and then recrystallized three times with 5 mL of ethanol to obtain 0.6 g of white solid. HCLC- 06C, purity: 99.8%, yield: 29%.

GC-MS：EI離子源m/z：354.3。 GC-MS: EI ion source m/z: 354.3.

實施例5Example 5

製備的化合物HCLC-06D的合成方法如下所示： The synthesis method of the prepared compound HCLC- 06D is as follows:

將1.47g的二氟二溴甲烷溶解在20mL無水四氫呋喃中，在-75至-80℃下，滴加2.28g三(二甲胺基)膦10mL無水四氫呋喃溶液，滴完後保持在-75至-80℃下反應0.5小時，升溫到室溫(25±3℃)，滴加1.2g化合物HCLC-06C-01的10mL四氫呋喃溶液，滴完後室溫(25±3℃)下反應2小時，於反應液中加入5mL 2M稀鹽酸，和20mL乙酸乙酯，分液，水相用10mL乙酸乙酯萃取兩次，有機相合併，用飽和碳酸氫鈉溶液洗滌三次，乾燥，濃縮得1.2g淺黃色固體，粗產物用石油醚沖提進行管柱層析，得到1g白色固體，再用2mL 乙醇再結晶兩次，得到0.5g白色固體HCLC-06D，純度：99.8%，產率：37.9%。 1.47 g of difluorodibromomethane was dissolved in 20 mL of anhydrous tetrahydrofuran, and 2.28 g of tris(dimethylamino)phosphine 10 mL of anhydrous tetrahydrofuran solution was added dropwise at -75 to -80 ° C, and kept at -75 to - after completion of the dropwise addition. The reaction was carried out at 80 ° C for 0.5 hour, and the temperature was raised to room temperature (25 ± 3 ° C). 1.2 g of the compound HCLC -06C-01 in 10 mL of tetrahydrofuran solution was added dropwise, and the reaction was carried out at room temperature (25 ± 3 ° C) for 2 hours after the dropwise addition. 5 mL of 2M dilute hydrochloric acid and 20 mL of ethyl acetate were added to the reaction mixture, and the mixture was separated, and the aqueous phase was extracted twice with 10 mL of ethyl acetate. The organic phase was combined, washed three times with saturated sodium hydrogen carbonate solution, dried and concentrated The solid and the crude product were subjected to column chromatography eluting with petroleum ether to give 1 g of white solid, and then recrystallized twice with 2 mL of ethanol to give 0.5 g of white solid HCLC -06D, purity: 99.8%, yield: 37.9%.

GC-MS：EI離子源m/z：376.2。 GC-MS: EI ion source m/z: 376.2.

實施例6Example 6

製備的化合物HCLC-06E的合成方法如下所示， The synthesis method of the prepared compound HCLC- 06E is as follows,

HCLC-06E-12參考文獻EP1160251合成。 HCLC -06E-12 is synthesized by reference EP 1160251.

用HCLC-06E-12替代HCLC-06-12，按照實施例1的方法即可得到化合物HCLC-06E。 Compound HCLC- 06E was obtained by the procedure of Example 1 by substituting HCLC -06E-12 for HCLC -06-12.

GC-MS：EI離子源m/z：374.3。 GC-MS: EI ion source m/z: 374.3.

1H NMR(300MHz,CDCl3),δ(ppm)：7.75(dd,J=14.9,10.0Hz,1H),7.47-7.16(m,4H),3.58-3.30(m,1H),2.76-2.49(m,4H),2.44-2.16(m,2H),2.09-1.75(m,3H),1.70-1.42(m,2H),1.33-1.17(m,2H),0.89(t,J=13.0Hz,3H)。 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.75 (dd, J = 14.9, 10.0 Hz, 1H), 7.47-7.16 (m, 4H), 3.58-3.30 (m, 1H), 2.76-2.49 (m,4H),2.44-2.16(m,2H),2.09-1.75(m,3H),1.70-1.42(m,2H),1.33-1.17(m,2H),0.89(t, J =13.0Hz , 3H).

實施例7Example 7

製備的化合物HCLC-06H的合成方法如下所示： The synthesis method of the prepared compound HCLC- 06H is as follows:

HCLC-06H-12參考文獻WO2009139330合成。 HCLC -06H-12 is synthesized by reference WO2009139330.

用HCLC-06H-12替代HCLC-06-12，按照實施例1的方法即可得到化合物HCLC-06H。 Compound HCLC- 06H was obtained by the procedure of Example 1 by substituting HCLC -06H-12 for HCLC -06-12.

GC-MS：EI離子源m/z：552.3。 GC-MS: EI ion source m/z: 552.3.

1H NMR(300MHz,CDCl3),δ(ppm)：7.75(dd,J=14.9,10.0Hz,1H),7.28-7.08(m,3H),6.95-6.86(m,3H),3.62-3.29(m,1H),2.75-2.49(m,4H),2.41-2.16(m,2H),2.11 -1.80(m,3H),1.61-1.49(m,2H),1.38-1.13(m,2H),0.89(t,J=13.0Hz,3H)。 1 H NMR (300MHz, CDCl 3 ), δ (ppm): 7.75 (dd, J = 14.9, 10.0 Hz, 1H), 7.28-7.08 (m, 3H), 6.95-6.86 (m, 3H), 3.62-3.29 (m, 1H), 2.75-2.49 (m, 4H), 2.41-2.16 (m, 2H), 2.11 - 1.80 (m, 3H), 1.61-1.49 (m, 2H), 1.38-1.13 (m, 2H) , 0.89 (t, J = 13.0 Hz, 3H).

下面實施例8是本發明液晶組合物的特性量測結果。 The following Example 8 is a measurement result of the characteristics of the liquid crystal composition of the present invention.

以下實施例中測試方法的簡寫代號如下： The shorthand code of the test method in the following examples is as follows:

Cp(℃)：澄清點(向列-各向同性相轉變溫度) Cp (°C): Clarification point (nematic-isotropic phase transition temperature)

η(mPa．s)：流動黏度(20℃，除非另有說明) η (mPa.s): flow viscosity (20 ° C, unless otherwise stated)

△n：光學各向異性(589nm，20℃) △n: optical anisotropy (589 nm, 20 ° C)

△ε：介電各向異性(1kHz，25℃) △ ε: dielectric anisotropy (1 kHz, 25 ° C)

實施例8Example 8

表2為HCLC-06、HCLC-06E和HCLC-06H配製成液晶組合物以及得到的相應性質。 Table 2 shows the liquid crystal compositions formulated with HCLC- 06, HCLC- 06E and HCLC- 06H and the corresponding properties obtained.

表2 液晶組合物配方和特性量測結果 Table 2 Liquid crystal composition formulation and characteristic measurement results

綜上所述，本發明通式(I)的含雙環[3.3.0]辛-7-烯結構的液晶化合物具有新穎結構，且具有較低黏度、較大的光學各向異性及較大的介電各向異性。本發明液晶組合物之功效在於使用通式(I)的液晶化合物，而可應用於各種顯示模式的液晶元件，故確實能達成本發明之目的。 In summary, the liquid crystal compound containing the bicyclo[3.3.0]oct-7-ene structure of the general formula (I) of the present invention has a novel structure and has a low viscosity, a large optical anisotropy and a large Dielectric anisotropy. The liquid crystal composition of the present invention has an effect of using the liquid crystal compound of the formula (I) and can be applied to liquid crystal elements of various display modes, so that the object of the present invention can be achieved.

惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the patent application and the patent specification of the present invention, All remain within the scope of the invention patent.

Claims (10)

一種含雙環[3.3.0]辛-7-烯結構的液晶化合物，具有通式(I)的結構： 其中，R1表示1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R1中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連； R2表示-H、-F、-Cl、-CN、-NCS、-SCN、-NCO、或1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R2中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-或-CH=CF-取代，其前提是雜原子彼此不直接連接； 環A1表示、或； 環A2、A3、和A4相同或不同，各自獨立地表示、 、、或的環狀結構； 其中，環A1、A2、A3、和A4代表的環狀結構還可以符合以下a)、b)、c)和d)中的至少一個：a)該環狀結構中的一個或多個氫原子可以被-D、-F、-Cl、-CN、-CF3、-OCF3、-CH2F、-OCH2F、-CF2H、-OCF2H、-OCH3或-CH3取代；b)該環狀結構中一個或多個-CH2-被-O-、-SiH2-、-S-或-CO-取代，其前提是雜原子彼此不直接連接；c)在該環狀結構中，芳環結構中的一個或多個-CH-可以被N取代； d)該環狀結構中一個或多個可以被取代；Z1表示-CF2O-、-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-C2H4OCH2-、-CH2CH2CH2O-或單鍵；Z2、Z3和Z4相同或不同，各自獨立地表示單鍵、-CF2O-、-CH2O-、-CH2CH2-、-CF2CH2-、-CF=CF-、-CH=CH-、-CH=CF-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CF2CF2CF2O-、-CH2CH2CF2O-、-OCF2CF2CF2-、-CH2CF2OCH2-、-CH=CHCF2O-、-CF2OCH=CH-、-CF2OCF=CH-、-CF2OCH=CF-、-CF=CFCF2O-、-CH=CFCF2O-、-CF2OCF=CF-、-CH=CHCH2CH2-、-C2H4OCH2-、-CH2CH=CHCH2-、-OCH2CH2CH2-、-CF=CF-CF=CF-、-C≡C-CF=CF-、-C≡C-CF=CF-C≡C-、 -CF=CF-C≡C-CF=CF-、-C≡C-CF2O-或-C≡C-，其中，在該Z2、Z3和Z4的鏈接基團中任意一個-CH2-可被-SiH2-取代；m、n和p相同或不同，各自獨立地表示0、1或2。當m為2，兩個Z2及兩個A2各自為相同或不同；當n為2，兩個Z3及兩個A3各自為相同或不同；當p為2，兩個Z4及兩個A4各自為相同或不同。 A liquid crystal compound containing a bicyclo[3.3.0]oct-7-ene structure having the structure of the general formula (I): Wherein R 1 represents a linear or branched alkyl or alkoxy group of 1 to 20 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 1 may be - O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the hetero atom Not directly connected to each other, and the O, S and Si atoms are not directly connected to the ring; R 2 represents -H, -F, -Cl, -CN, -NCS, -SCN, -NCO, Or a straight or branched alkyl or alkoxy group having 1 to 20 carbon atoms substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 2 may be -O-, - S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF- or -CH=CF-substitution, provided that the heteroatoms are not directly connected to each other; ring A 1 represents , or ; Rings A 2 , A 3 , and A 4 are the same or different and each independently represents , , , or The cyclic structure represented by the rings A 1 , A 2 , A 3 , and A 4 may also conform to at least one of the following a), b), c), and d): a) the ring One or more hydrogen atoms in the structure may be -D, -F, -Cl, -CN, -CF 3 , -OCF 3 , -CH 2 F, -OCH 2 F, -CF 2 H, -OCF 2 H , -OCH 3 or -CH 3 substituted; b) one or more -CH 2 - in the cyclic structure is substituted by -O-, -SiH 2 -, -S- or -CO-, provided that the heteroatoms are Not directly connected; c) in the cyclic structure, one or more -CH- in the aromatic ring structure may be substituted by N; d) one or more of the cyclic structures Can be Substituted; Z 1 represents -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 ) 4 -, -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -C 2 H 4 OCH 2 -, -CH 2 CH 2 CH 2 O- or a single bond; Z 2 , Z 3 and Z 4 are the same or different, each Independently represents a single bond, -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF 2 CH 2 -, -CF=CF-, -CH=CH-, -CH=CF-, -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 -, -OCF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CH 2 CH 2 CF 2 O-, -OCF 2 CF 2 CF 2 -, -CH 2 CF 2 OCH 2 -, -CH=CHCF 2 O-, -CF 2 OCH=CH-, -CF 2 OCF=CH-, -CF 2 OCH=CF-, -CF=CFCF 2 O-, -CH=CFCF 2 O-, -CF 2 OCF=CF-, -CH=CHCH 2 CH 2 -, -C 2 H 4 OCH 2 -, -CH 2 CH=CHCH 2 - , -OCH 2 CH 2 CH 2 -, -CF=CF-CF=CF-, -C≡C-CF=CF-, -C≡C-CF=CF-C≡C-, -CF=CF-C ≡C-CF=CF-, -C≡C-CF 2 O- or -C≡C-, wherein any one of the linking groups of Z 2 , Z 3 and Z 4 -CH 2 - can be - SiH 2 -substituted; m, n and p are the same or different and each independently represents 0, 1 or 2. When m is 2, two Z 2 and two A 2 are the same or different; when n is 2, two Z 3 and two A 3 are the same or different; when p is 2, two Z 4 and The two A 4 are each the same or different. 如請求項1所述的液晶化合物，其中，m、n和p相同或不同，各自獨立地表示0、1或2，且m+n+p4。 The liquid crystal compound according to claim 1, wherein m, n and p are the same or different, each independently represents 0, 1 or 2, and m+n+p 4. 如請求項1所述的液晶化合物，其中，該液晶化合物表示 或 其中，R1表示1-5個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R1中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-、-CH=CF-、-COO-或-OCO-取代，其前提是雜原子彼此不直接連接，並且O、S和Si原子不與環直接相連；R2表示-H、-F、-CN和1-5個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基，其中，在該R2中至少一個-CH2-可以被-O-、-CH=CH-、-C≡C-、-CF=CF-或-CH=CF-取代，其前提是雜原子彼此不直接連接；Z1表示-CH2O-、-CH2CH2-、-CH2CF2-、-CF2CH2-、-(CH2)4-、-CH2CH2CF2O-、-CH2CF2OCH2-、-CH2CH2CH2O-或單鍵；Z2、Z3、和Z4相同或不同，各自獨立地表示-CF2O-、-CH2O-、-CH2CH2-、-CF=CF-、-CH=CH-、-C2F4-、-OCF2CF2O-、-CF=CFCF2O-、-C≡C-或單鍵；L1~L4各自獨立地表示-H、-F或-CH3；L5~L16各自獨立地表示-H、-F、-OCF2H、-CH3、-OCH3、-OCF3或-CF3。 The liquid crystal compound according to claim 1, wherein the liquid crystal compound is represented by or Wherein R 1 represents a straight or branched alkyl or alkoxy group of 1 to 5 carbon atoms which is substituted or unsubstituted with at least one halogen, wherein at least one -CH 2 - in the R 1 may be - O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF-, -CH=CF-, -COO- or -OCO-substitution, provided that the hetero atom Not directly connected to each other, and the O, S and Si atoms are not directly bonded to the ring; R 2 represents -H, -F, -CN and a straight or branched chain of 1-5 carbon atoms substituted or unsubstituted by at least one halogen An alkyl or alkoxy group of a chain wherein at least one -CH 2 - in the R 2 may be -O-, -CH=CH-, -C≡C-, -CF=CF- or -CH=CF a substitution, provided that the heteroatoms are not directly bonded to each other; Z 1 represents -CH 2 O-, -CH 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CH 2 -, -(CH 2 ) 4 - , -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -CH 2 CH 2 CH 2 O- or a single bond; Z 2 , Z 3 , and Z 4 are the same or different and each independently represents -CF 2 O-, -CH 2 O-, -CH 2 CH 2 -, -CF=CF-, -CH=CH-, -C 2 F 4 -, -OCF 2 CF 2 O-, -CF=CFCF 2 O-, -C≡C- or a single bond; L 1 ~ L 4 each independently represent -H, -F or -CH 3 ; L 5 ~L 16 each independently represents -H, -F, -OCF 2 H, -CH 3 , -OCH 3 , -OCF 3 or -CF 3 . 一種液晶組合物，包含至少一種如請求項1至3中任一 項所述的液晶化合物。 A liquid crystal composition comprising at least one of claims 1 to 3 The liquid crystal compound described in the above. 如請求項4所述的液晶組合物，其中，該液晶組合物包括一種至五種如請求項1至3中任一項所述的液晶化合物。 The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises one to five liquid crystal compounds according to any one of claims 1 to 3. 如請求項4所述的液晶組合物，其中，該液晶組合物還包含至少一種通式(Ⅱ)的液晶化合物： 其中，R3和R4相同或不同，各自獨立地表示-H、-F、-Cl、-CN、-OCHCF2、1-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烷基或烷氧基、或2-20個碳原子經至少一個鹵素取代或未經取代的直鏈或支鏈的烯基或烯氧基，其中，在該R3和該R4中至少一個-CH2-可以被-O-、-S-、-SiH2-、-CH=CH-、-C≡C-、-CF=CF-或-CH=CF-取代，其前提是雜原子彼此不直接連接；B1、B2、B3和B4相同或不同，各自獨立地表示、 、1,4-伸苯基、2,3-二氟-1,4-伸苯基、3-氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2-氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基或萘-2,6-二 基，其中該或中的H可以獨立地被CN 或鹵素取代；該中的一個或兩個不相鄰的-CH2- 可以被-O-或-S-取代，該上任意一個或多個的 H可以各自獨立地被F取代；該中的一個或兩 個不相鄰的-CH-可以被N取代，該上一個或多個中任意的H可以各自獨立地被F取代；；Y1、Y2、Y3和Y4相同或不同，各自獨立地表示-CF2O-、-CH2O-、-OCH2-、-CH2CH2-、-CF2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-(CH2)3O-、-O(CH2)3-、-C2F4-、-(CH2)4-、-C4F8-、-OCF2CF2O-、-CF2CF2CF2O-、-CH2CH2CF2O-、-CH2CF2OCH2-、-C2H4OCH2-、-OCH2CH2CH2-或單鍵，其中，在該Y1和Y2中的任意一個-CH2-可被-SiH2-取代；a、b、c和d相同或不同，各自獨立地表示0、1或2。當a為2，兩個B1及Y1各自為相同或不同；當b為2，兩個B2及Y2各自為相同或不同；當c為2，兩個B3及Y3各自為相同或不同；及當d為2，兩個B4及Y4各自為相同或不同。 The liquid crystal composition according to claim 4, wherein the liquid crystal composition further comprises at least one liquid crystal compound of the formula (II): Wherein R 3 and R 4 are the same or different and each independently represents -H, -F, -Cl, -CN, -OCHCF 2 , a straight chain of 1-20 carbon atoms substituted or unsubstituted with at least one halogen or a branched alkyl or alkoxy group, or a linear or branched alkenyl or alkenyloxy group having 2 to 20 carbon atoms substituted or unsubstituted with at least one halogen, wherein R 3 and R 4 are At least one -CH 2 - may be substituted by -O-, -S-, -SiH 2 -, -CH=CH-, -C≡C-, -CF=CF- or -CH=CF-, provided that The heteroatoms are not directly connected to each other; B 1 , B 2 , B 3 and B 4 are the same or different and each independently represents , , 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-benzene Base, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene or naphthalene-2,6- Two bases, where or H in can be independently replaced by CN or halogen; One or two of the non-adjacent -CH 2 - may be replaced by -O- or -S-, Any one or more of H may be independently replaced by F; One or two non-adjacent -CH- in the middle may be replaced by N, Any of the above H or any of H may be independently substituted by F;; Y 1 , Y 2 , Y 3 and Y 4 are the same or different and each independently represents -CF 2 O-, -CH 2 O-, - OCH 2 -, -CH 2 CH 2 -, -CF 2 CH 2 -, -CH(CH 3 )CH 2 -, -CH 2 CH(CH 3 )-, -(CH 2 ) 3 O-, -O ( CH 2 ) 3 -, -C 2 F 4 -, -(CH 2 ) 4 -, -C 4 F 8 -, -OCF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CH 2 CH 2 CF 2 O-, -CH 2 CF 2 OCH 2 -, -C 2 H 4 OCH 2 -, -OCH 2 CH 2 CH 2 - or a single bond, wherein any one of Y 1 and Y 2 - CH 2 - may be substituted by -SiH 2 -; a, b, c and d are the same or different and each independently represents 0, 1 or 2. When a is 2, two B 1 and Y 1 are the same or different; when b is 2, two B 2 and Y 2 are the same or different; when c is 2, two B 3 and Y 3 are each The same or different; and when d is 2, the two B 4 and Y 4 are the same or different. 如請求項6所述的液晶組合物，其中，以該液晶組合物的總重量為100wt%，該通式(I)化合物的用量範圍為5至50wt%，及該通式(Ⅱ)化合物的用量範圍為50至95wt%。 The liquid crystal composition according to claim 6, wherein the compound of the formula (I) is used in an amount ranging from 5 to 50% by weight based on the total weight of the liquid crystal composition, and the compound of the formula (II) The amount ranges from 50 to 95% by weight. 如請求項6所述的液晶組合物，其中，以該液晶組合物的總重量為100wt%，該通式(I)化合物的用量範圍為10至30wt%，及該通式(Ⅱ)化合物的用量範圍為70至90wt%。 The liquid crystal composition according to claim 6, wherein the compound of the formula (I) is used in an amount ranging from 10 to 30% by weight based on the total weight of the liquid crystal composition, and the compound of the formula (II) The amount ranges from 70 to 90% by weight. 如請求項6所述的液晶組合物，其中，該通式(Ⅱ)的液晶化合物表示 The liquid crystal composition according to claim 6, wherein the liquid crystal compound of the formula (II) is represented by 一種液晶顯示器，包含如請求項4至9中任一項所述的液晶組合物。 A liquid crystal display comprising the liquid crystal composition according to any one of claims 4 to 9.
TW102136566A 2012-10-13 2013-10-09 A liquid crystal compound having bicyclo[3.3.0] octyl-7-ene-based structure, a liquid crystal composition comprising said compound and applicaton thereof TWI608086B (en)

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